EP1755890B1 - Mehrschichtfolie - Google Patents
Mehrschichtfolie Download PDFInfo
- Publication number
- EP1755890B1 EP1755890B1 EP05756778A EP05756778A EP1755890B1 EP 1755890 B1 EP1755890 B1 EP 1755890B1 EP 05756778 A EP05756778 A EP 05756778A EP 05756778 A EP05756778 A EP 05756778A EP 1755890 B1 EP1755890 B1 EP 1755890B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- abs
- layer
- adhesion promoter
- gew
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 0 CC(C)(*)C(N(*)C(C(*)(*C1*C1)N)=O)=O Chemical compound CC(C)(*)C(N(*)C(C(*)(*C1*C1)N)=O)=O 0.000 description 4
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
- B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2377/00—Polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
Definitions
- the subject of the present invention is a multilayer film which contains at least one layer of a polyamide (PA) and a special adhesion promoter and which is suitable for bonding with ABS as substrate material.
- PA polyamide
- a suggestion to remedy this is the use of multilayer plastic films, which are used to cover the components and no longer need to be painted.
- the bond between substrate and decorating film can be realized by a number of manufacturing processes.
- the film can be pressed, for example, with the substrate or you can choose a Schuspritzmaschine, in which the film is inserted in the component manufacturing in the injection mold.
- the concept of a foil as a decor carrier also meets a trend towards the individualization of design elements on the automobile. This tendency leads namely in the production of a larger range of models, but which is reduced in the number of each manufactured components per series. Since the use of foils allows fast, easy design changes, this challenge can be met. It is important here that the film meets the standards required in the automotive industry with respect to surface properties (Class A surface), resistance to media and visual impression.
- Such decorative films are known in principle.
- the EP 0 949 120 A1 describes decorative films with polyalkyl methacrylate as the base layer, which may also contain a substrate-side support layer of polyamide, while from the WO 94/03337 Decorative films are known whose base layer may consist of a variety of alternative polymers, including polyamide.
- polyamides Due to their property profile, such as impact resistance and chemical resistance, are polyamides, in particular polyamides based on PA12 or PA612, for the production of such decorative films well suited coating systems show in principle a tendency to brittle fracture behavior. If a plastic component decorated in this form is subjected to impact stress, propagation of the crack from the lacquer layer into the underlying substrate occurs, which leads to deeper-reaching damage. In contrast, the use of cold-impact-resistant materials in a decorative film covering the substrate, on the other hand, avoids damage to the outer skin and the substrate. It should be noted that in the same course a sufficient chemical resistance, in particular to fuels, oils and fats, must be realized. These requirements are met by polyamides such as PA 12, PA 11 or PA 612.
- polyamides containing aliphatic structures show a favorable UV aging behavior. This means that there is little yellowing tendency that can not lead to undesirable color changes over the lifetime of an automobile. This combination of properties is not representable in other plastics.
- the suitability of such a film must also be taken into account with regard to economically advantageous processing methods.
- the good thermoforming behavior should be emphasized here. This results from an inherently high elongation at break of the polyamide materials, which sets them apart from other materials
- the task in the overall context of the application is the discovery of a suitable adhesion promoter, which allows the connection of the polyamide layer to the substrate.
- a commonly used substrate material is ABS or its blend with polycarbonate (PC), which in some cases is reinforced by glass fibers or other fillers.
- the adhesion promoter must be suitable for being processed in a coextrusion process to form a layer within a multilayer film.
- the composite of this multilayer film with the substrate material can then be produced for example by injection molding or pressing. Both in the coextrusion for multilayer film as well as in the back molding or pressing is that here increased demands on the adhesion of the primer are made because there is no forced mixing of the components, the continuous reaction of a complete reactive amine groups on the Phase interface allows.
- the temperature in the contact zone of the joining partners for example, when backmolding is high enough for a short time to achieve a composite formation.
- the two aforementioned documents offer no solution to this problem.
- the US 3 561 493 discloses that two layers of different polymers can be coextruded through an intermediate layer consisting of a blend of these polymers. However, this teaching is not transferable to the system polyamide / ABS. The statement of US 3 561 493 only applies to a multilayer pipe system in which a polyethylene layer with a PA 11 is adhered by the use of a blend of both materials. Attempting to translate this teaching to the bonding between polyamide or a polyether block amide derived therefrom and ABS failed because no composition could be found that would provide sufficient, reliable adhesion to both materials.
- the US 4 301 216 describes multi-layer composites of a polyamide layer, an ABS layer and in between a primer layer of carboxylated SAN or ABS.
- adhesion promoters are not commercially available.
- the polyamide of the layer according to I. is subject to no restriction.
- Aliphatic homo- and copolycondensates are suitable in this case, for example PA46, PA66, PA88, PA610, PA612, PA810, PA1010, PA1012, PA1212, PA6, PA7, PA8, PA9, PA10, PA11 and PA12 Labeling of the polyamides is in accordance with international standards, where the first digit (s) indicate the C atomic number of the starting diamine and the last digit (s) the C atomic number of the dicarboxylic acid in that an ⁇ , ⁇ -aminocarboxylic acid or the lactam derived therefrom has been used, for the rest reference is made to H. Domininghaus, Die Kunststoffe und Struktur, pages 272 ff., VDI-Verlag, 1976.)
- copolyamides are used, these z.
- adipic acid, sebacic acid, suberic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, etc. as co-acid or bis (4-aminocyclohexyl) methane, trimethylhexamethylenediamine, hexamethylenediamine or the like as codiamine.
- Lactams such as caprolactam or laurolactam
- aminocarboxylic acids such as ⁇ -aminoundecanoic acid can likewise be incorporated as cocomponent.
- polyamides and mixed aliphatic / aromatic polycondensates are suitable, as z. Tie U.S. Patent No. 2,071,250 . 2 071 251 . 2 130 523 . 2,130,948 . 2 241 322 . 2 312 966 . 2 512 606 and 3 393 210 as in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Vol. 18, pp. 328 et seq. And 435 et seq., Wiley & Sons, 1982 , to be discribed.
- Further suitable polyamides are poly (etheresteramides) or poly (etheramides); Such products are z. Tie DE-OSS 25 23 991 . 27 12 987 and 30 06 961 described.
- the polyamide molding composition may contain either one of these polyamides or more as a mixture. Furthermore, up to 40% by weight of other thermoplastics may be present, provided that they do not interfere with the bondability, in particular impact-modifying rubbers such as ethylene / propylene or ethylene / propylene / diene copolymers (US Pat. EP-A-0295076 ), Poly-pentenylene, polyoctenylene, random or block copolymers of alkenylaromatic compounds with aliphatic olefins or dienes (US Pat.
- EP-A-0 261 748 or core / shell rubbers having a viscoelastic core of (meth) acrylate, butadiene or styrene / butadiene rubber with glass transition temperatures Tg ⁇ -10 ° C, the core may be crosslinked and the shell of styrene and / or methyl methacrylate and / or further unsaturated monomers can be constructed ( DE-OSS 21 44 528 . 37 28 685 ).
- the polyamide molding compound the usual additives for polyamides and additives such.
- additives such as flame retardants, stabilizers, plasticizers, processing aids, fillers, in particular for improving the electrical conductivity, reinforcing fibers, pigments or the like may be added.
- the amount of the said agents should be metered so that the desired properties are not seriously affected.
- the monomer units of the polyamide derived from diamine, dicarboxylic acid or lactam (or aminocarboxylic acid) have on average at least 8 C atoms and more preferably at least 9 C atoms.
- the layer of the polyamide molding composition can be prepared by all technically common methods, particularly advantageously by extrusion or coextrusion.
- ABS polymers have long been state of the art and are available in the form of many types of trade. They are composed essentially of acrylonitrile, butadiene and styrene; This three-monomer system can be widely varied to meet the respective requirements.
- the polymer contains chains of polybutadiene, polyisoprene, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR) or the like onto which styrene or preferably a styrene-acrylonitrile mixture has been grafted; the mixture may additionally contain other comonomers such. As methyl methacrylate.
- the rubber content is from 5 to 30 wt .-%;
- the matrix of styrene-acrylonitrile copolymer usually contains 10 to 45 wt .-% and in particular 15 to 35 wt .-% of acrylonitrile. Due to the production, at least part of this copolymer is grafted onto the rubber while the remainder is in free form.
- the ABS molding compound may contain the usual additives such. As plasticizers, processing aids, flame retardants, stabilizers, antistatic agents, fillers, pigments and reinforcing agents. In addition, the ABS molding compound may contain other thermoplastics as constituents, such as polycarbonates, polyamides or polyesters.
- the units of the formula (I) are derived, for example, from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate or isobutyl methacrylate.
- the units of the formula (II) are derived, for example, from acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide or N, N-dimethylacrylamide.
- the units of the formula (III) are derived from acrylonitrile or methacrylonitrile.
- maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide or N-methylaconitic imide.
- the units of the formula (VI) are derived from optionally substituted maleic anhydrides, such as maleic anhydride or aconitic anhydride. The latter may be wholly or partly by other unsaturated acid anhydrides such. B. itaconic anhydride are replaced, which have the same effect.
- the units of the formula (VII) are derived from glycidyl acrylate or glycidyl methacrylate and the units of the formula (VIII) are from vinyloxazoline or isopropenyloxazoline.
- the copolymer may in each case additionally contain further monomer units, for example those derived from maleic diesters, fumaric diesters, itaconic esters, vinyl acetate or ethene, as long as the desired adhesion-promoting effect is not significantly impaired thereby.
- the adhesion promoter may consist entirely of the copolymer; in a variant thereof, the copolymer contains a Schlagzähmodifier, z. B. an acrylate rubber.
- the adhesion promoter contains 2 to 99.9 wt .-%, preferably 3 to 80 wt .-%, particularly preferably 4 to 60 wt .-% and particularly preferably 5 to 40 wt .-% of the copolymer and 0, 1 to 98 wt .-%, preferably 20 to 97 wt .-%, particularly preferably 40 to 96 wt .-% and particularly preferably 60 to 95 wt .-% ABS.
- the adhesion promoter contains 2 to 99.9 wt .-%, preferably 3 to 80 wt .-%, particularly preferably 4 to 60 wt .-% and particularly preferably 5 to 40 wt .-% of the copolymer and 0, 1 to 98 wt .-%, preferably 20 to 97 wt .-%, particularly preferably 40 to 96 wt .-% and particularly preferably 60 to 95 wt .-% polyamide.
- an impact modifier such. B. contain an EPM rubber.
- the adhesion promoter contains 2 to 99.8 wt .-%, preferably 3 to 80 wt .-%, particularly preferably 4 to 60 wt .-% and particularly preferably 5 to 40 wt .-% of the copolymer and 0.1 to 97.9 wt .-%, preferably 5 to 92 wt .-%, particularly preferably 10 to 86 wt .-% and particularly preferably 20 to 75 wt .-% ABS and additionally 0.1 to 97.9 wt .-%, preferably 5 to 92 wt .-%, particularly preferably 10 to 86 wt .-% and particularly preferably 20 to 75 wt .-% polyamide.
- the primer can the usual auxiliaries and additives such. As flame retardants, stabilizers, plasticizers, processing aids, pigments or the like. The amount of the said agents should be metered so that the desired properties are not seriously affected.
- the invention furthermore relates to multilayer films which contain at least one layer of a polyamide molding composition and at least one layer of the adhesion promoter according to the invention, as well as composite parts which are composed of such a multilayer film and a part of an ABS molding composition.
- the film in addition to the layers of a polyamide molding composition according to the invention and the claimed adhesion promoter, the film, depending on the application, contain other layers, for example, a substrate-side support layer of an ABS molding composition, a color layer, a functional layer, another polyamide layer and / or a cover layer or a clearcoat.
- the color layer may be a lacquer layer; However, it is, according to the prior art, preferably from a colored thermoplastic layer.
- the thermoplastic may be a polyamide or a polymer that is compatible with polyamide.
- colorants organic dyes or inorganic or organic pigments can be used.
- the functional layer is a layer which, depending on the application requirements, makes the properties of the film positive independent of the color, for example with regard to the mechanical properties or the resistance, for example to UV or heat. It may consist of any molding compound which meets the application requirements and has the required adhesion to the adjacent layers, for example of polyamide, polyester or polycarbonate.
- the clearcoat may, for example, consist of polyamide, an acrylate polymer, a fluoropolymer or mixtures thereof, according to the prior art. It should ensure the required visual surface properties and protect the underlying layers.
- the multilayer film can be produced, for example, by coextrusion or lamination, optionally followed by a processing method such as reshaping, painting or surface treatment (for example by means of plasma treatment) according to the prior art.
- a peelable protective film can be laminated onto the finished multilayer film, which acts as a transport or assembly protection and is removed after the production of the composite part.
- the film according to the invention is particularly suitable for meeting the requirements placed on materials for decorative films in the field of automobile exterior and interior.
- the claimed adhesion promoter ensures a reliably adhering connection between the polyamide layer and ABS as frequently encountered substrate material. This applies both to cases in which ABS is brought into contact with the adhesion promoter by means of injection molding, and to cases in which ABS is extruded onto the adhesion promoter, for example in a coextrusion, or where the composite is produced by pressing, lamination, backpressing or backfoaming is produced. Adhesion is ensured even if the film is subjected to a forming process, for example thermoforming, before the injection molding, or if the composite part is formed after production.
- the molding compositions were prepared with a automatic kneader ZCM 41/46 - 21D, wherein the melt temperature was 250 ° C, the mass flow rate 12 kg / h and the speed 250 min -1 .
- the multilayer films were produced on a Collin plant at a take-off speed of 2.5 m / min.
- the extruded monolayers were combined and passed over a calender.
- the films had a width of 24 cm.
- the back injection was done on an Engel ES600 / 150 machine with a tool temperature of 80 ° C and a melt temperature of 280 ° C.
- the film was cut to a size of 100 mm x 150 mm and placed in a tool (plate 105 mm x 150 mm x 0.8 - 10 mm).
- the thickness of the back-injected plate was 3 mm including the foil
- a test specimen measuring 10 mm ⁇ 130 mm was punched out of the plate and subjected to a peel test.
- a test specimen was punched out of the multilayer film with the same dimensions and the same pattern was used.
- one end of the test piece was stored in hot polyethylene glycol for 30 minutes for separation. After separation, the test specimen was clamped with the layers to be separated at an angle of 180 ° in the chuck of the testing machine.
- the chucks drove apart at a speed of 50 mm / min, and the test piece was subjected to a strong peel load.
- the separation resistance that the composite presented with this peel stress was recorded. This was done by measuring the separation force in N necessary for the separation. The separation resistance was determined from this by the measured separation force was set by forming the quotient in relation to the sample width. The sample width was in all cases 10 mm, so that the separation resistance carries the unit N / mm. It is considered sufficient if it is at least 3 N / mm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Thin Magnetic Films (AREA)
- Optical Filters (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200410029217 DE102004029217A1 (de) | 2004-06-16 | 2004-06-16 | Mehrschichtfolie |
PCT/EP2005/052675 WO2005123384A1 (de) | 2004-06-16 | 2005-06-09 | Mehrschichtfolie |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1755890A1 EP1755890A1 (de) | 2007-02-28 |
EP1755890B1 true EP1755890B1 (de) | 2008-09-10 |
Family
ID=34971560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05756778A Not-in-force EP1755890B1 (de) | 2004-06-16 | 2005-06-09 | Mehrschichtfolie |
Country Status (11)
Country | Link |
---|---|
US (2) | US20070166560A1 (ko) |
EP (1) | EP1755890B1 (ko) |
JP (1) | JP4598066B2 (ko) |
KR (1) | KR101216760B1 (ko) |
CN (1) | CN1968812B (ko) |
AT (1) | ATE407797T1 (ko) |
BR (1) | BRPI0512077B1 (ko) |
DE (2) | DE102004029217A1 (ko) |
ES (1) | ES2314673T3 (ko) |
RU (1) | RU2381104C2 (ko) |
WO (1) | WO2005123384A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3640287A1 (de) | 2018-10-16 | 2020-04-22 | Röhm GmbH | Polyetherblockamid-poly(meth)acrylat-schäume |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE50309009D1 (de) * | 2002-09-21 | 2008-03-06 | Evonik Degussa Gmbh | Verfahren zur Herstellung eines dreidimensionalen Objektes |
EP1459871B1 (de) * | 2003-03-15 | 2011-04-06 | Evonik Degussa GmbH | Verfahren und Vorrichtung zur Herstellung von dreidimensionalen Objekten mittels Mikrowellenstrahlung sowie dadurch hergestellter Formkörper |
DE10334496A1 (de) * | 2003-07-29 | 2005-02-24 | Degussa Ag | Laser-Sinter-Pulver mit einem Metallsalz und einem Fettsäurederivat, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver |
DE102004010162A1 (de) | 2004-02-27 | 2005-09-15 | Degussa Ag | Polymerpulver mit Copolymer, Verwendung in einem formgebenden Verfahren mit nicht fokussiertem Energieeintrag und Formkörper, hergestellt aus diesem Polymerpulver |
DE102004012682A1 (de) * | 2004-03-16 | 2005-10-06 | Degussa Ag | Verfahren zur Herstellung von dreidimensionalen Objekten mittels Lasertechnik und Auftragen eines Absorbers per Inkjet-Verfahren |
DE102004020453A1 (de) | 2004-04-27 | 2005-11-24 | Degussa Ag | Polymerpulver mit Polyamid, Verwendung in einem formgebenden Verfahren und Formkörper, hergestellt aus diesem Polymerpulver |
DE102004020452A1 (de) * | 2004-04-27 | 2005-12-01 | Degussa Ag | Verfahren zur Herstellung von dreidimensionalen Objekten mittels elektromagnetischer Strahlung und Auftragen eines Absorbers per Inkjet-Verfahren |
DE102004024440B4 (de) | 2004-05-14 | 2020-06-25 | Evonik Operations Gmbh | Polymerpulver mit Polyamid, Verwendung in einem formgebenden Verfahren und Formkörper, hergestellt aus diesem Polymerpulver |
DE102004047876A1 (de) * | 2004-10-01 | 2006-04-06 | Degussa Ag | Pulver mit verbesserten Recyclingeigenschaften, Verfahren zu dessen Herstellung und Verwendung des Pulvers in einem Verfahren zur Herstellung dreidimensionaler Objekte |
DE102004062761A1 (de) * | 2004-12-21 | 2006-06-22 | Degussa Ag | Verwendung von Polyarylenetherketonpulver in einem dreidimensionalen pulverbasierenden werkzeuglosen Herstellverfahren, sowie daraus hergestellte Formteile |
DE102004063220A1 (de) * | 2004-12-29 | 2006-07-13 | Degussa Ag | Transparente Formmassen |
DE102005002930A1 (de) * | 2005-01-21 | 2006-07-27 | Degussa Ag | Polymerpulver mit Polyamid, Verwendung in einem formgebenden Verfahren und Formkörper, hergestellt aus diesem Polymerpulver |
DE102005007035A1 (de) * | 2005-02-15 | 2006-08-17 | Degussa Ag | Verfahren zur Herstellung von Formteilen unter Erhöhung der Schmelzesteifigkeit |
DE102005007663A1 (de) | 2005-02-19 | 2006-08-24 | Degussa Ag | Transparente, dekorierbare mehrschichtige Folie |
DE102005007665A1 (de) * | 2005-02-19 | 2006-08-31 | Degussa Ag | Folie auf Basis eines Polyamidblends |
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-
2004
- 2004-06-16 DE DE200410029217 patent/DE102004029217A1/de not_active Withdrawn
-
2005
- 2005-06-09 EP EP05756778A patent/EP1755890B1/de not_active Not-in-force
- 2005-06-09 US US10/589,264 patent/US20070166560A1/en not_active Abandoned
- 2005-06-09 KR KR1020067026470A patent/KR101216760B1/ko active IP Right Grant
- 2005-06-09 JP JP2007515938A patent/JP4598066B2/ja not_active Expired - Fee Related
- 2005-06-09 WO PCT/EP2005/052675 patent/WO2005123384A1/de active IP Right Grant
- 2005-06-09 DE DE200550005337 patent/DE502005005337D1/de active Active
- 2005-06-09 BR BRPI0512077-2A patent/BRPI0512077B1/pt not_active IP Right Cessation
- 2005-06-09 CN CN2005800198717A patent/CN1968812B/zh not_active Expired - Fee Related
- 2005-06-09 ES ES05756778T patent/ES2314673T3/es active Active
- 2005-06-09 RU RU2007100929A patent/RU2381104C2/ru not_active IP Right Cessation
- 2005-06-09 AT AT05756778T patent/ATE407797T1/de not_active IP Right Cessation
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3640287A1 (de) | 2018-10-16 | 2020-04-22 | Röhm GmbH | Polyetherblockamid-poly(meth)acrylat-schäume |
Also Published As
Publication number | Publication date |
---|---|
EP1755890A1 (de) | 2007-02-28 |
ATE407797T1 (de) | 2008-09-15 |
JP2008502758A (ja) | 2008-01-31 |
CN1968812A (zh) | 2007-05-23 |
KR101216760B1 (ko) | 2012-12-31 |
JP4598066B2 (ja) | 2010-12-15 |
DE502005005337D1 (de) | 2008-10-23 |
ES2314673T3 (es) | 2009-03-16 |
CN1968812B (zh) | 2013-06-12 |
KR20070033996A (ko) | 2007-03-27 |
US20070166560A1 (en) | 2007-07-19 |
RU2381104C2 (ru) | 2010-02-10 |
WO2005123384A1 (de) | 2005-12-29 |
US20100221551A1 (en) | 2010-09-02 |
DE102004029217A1 (de) | 2006-01-05 |
BRPI0512077B1 (pt) | 2017-12-26 |
RU2007100929A (ru) | 2008-07-27 |
BRPI0512077A (pt) | 2008-02-06 |
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